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At least 55 records · Page 3

Mass spectrometry in structural and stereochemical problems. CXCIX.

Electron-impact induced fragmentations of o-, m-, and p-hydroxyalkylphenones and their trimethylsilyl (TMS) ethers are studied by means of high-resolution mass spectrometry, metastable defocusing, and deuterium labeling of the TMS ether derivatives. A markedly increased methyl radical loss from the o-TMS ether is attributed to a proximity effect. Minor fragmentation was observed with m- and p-isomers. Significantly intense doubly-charged ions were formed from ketonic cleavage and by the loss of a TMS methyl radical. The sequence of fragmentation was found to depend on the size of the alkyl group attached to the ketone carbonyl.

Smith, G. G.↗

Study of the organic matter in the DSDP /JOIDES/ cores, legs 10-15

The composition of the organic matter collected on legs 10 to 15 of the DSDP (Deep Sea Drilling Project) is described. Distributions of various alkanes, carboxylic acids, steroids and terpenoids, isoprenoid ketones and olefins, and aromatic polycyclic compounds are given. Samples analyzed had terrigenous clay components, with variable organic carbon contents and thus diverse solvent soluble matter. The distribution patterns for the various compound series monitored were of marine derivation, with the terrigenous components superimposed. Diagenesis of steroids appeared to proceed via both stanones and stanols to their respective steranes. Degradative processes were observed to be operative: oxidative products, mainly ketones derived from steroids and phytol, were identified, probably due to microbial alteration prior to or during sedimentation. Loss of alkane and fatty acid C preferences and presence of polycyclic aromatics evinced maturation. Results indicate that the accumulation, degradation, diagenesis and maturation of organic matter occurs in various steps in the deep sea environment.

Simoneit, B. R. T.↗

Evaluation of performance impairment by spacecraft contaminants

The environmental contaminants (isolated as off-gases in Skylab and Apollo missions) were evaluated. Specifically, six contaminants were evaluated for their effects on the behavior of juvenile baboons. The concentrations of contaminants were determined through preliminary range-finding studies with laboratory rats. The contaminants evaluated were acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), trichloroethylene (TCE), heptane and Freon 21. When the studies of the individual gases were completed, the baboons were also exposed to a mixture of MEK and TCE. The data obtained revealed alterations in the behavior of baboons exposed to relatively low levels of the contaminants. These findings were presented at the First International Symposium on Voluntary Inhalation of Industrial Solvents in Mexico City, June 21-24, 1976. A preprint of the proceedings is included.

Geller, I.↗

Sulfur poisoning of hydrocarbon oxidation by palladium

Using a differential bed recycle reactor the oxidation of ethane and diethyl ketone by a Pd catalyst was studied at the 0-30 ppm level in air. In both cases first order kinetics were observed. The ethane oxidation rate was characterized n the Arrhenius form by a pre-exponential of 1.0 x 10 to the 8th power cm/sec and an E sub a of 27 kcal/mole. The diethyl ketone oxidation rate was characterized by a pre-exponential of 5.7 x -1000 cm/sec and E sub a of 14 kcal/mole. Poisoning of ethan oxidation was also investigated by hydrogen sulfide and to a smaller extent by the refrigerants Freon 22 and Gentron 142-B. Poisoning by Gentron 142-B was much more severe than by hydrogen sulfide. Kinetic experiments indicated that only the pre-exponential was changing.

Baumgartner, A. J.↗

Toughening of BIS maleimide resins: Synthesis and characterization of maleimide terminated poly(arylene ether) oligomers and polymers

Amine functional poly(arylene ether) sulfones were previously reported. Herein, the chemistry was extended to amorphous poly(arylene ether) ketones because of their higher fracture toughness values, relative to the polysulfones. It was demonstrated that the amino functional oligomers undergo a self-crosslinking reaction at temperatures above about 220 C. This produces an insoluble, but ductile network that has excellent resistance. A ketamine structure hypothesis was proposed and verified using solid state magic angle NMR. In most cases, the water generated upon ketamine formation is too low to produce porosity and solid networks are obtained. The stability of the ketamine networks towards hydrolysis is excellent. The chemistry was further demonstrated to be able to crosslink preformed nonfunctional poly(arylene ether) ketones if a difunctional amine was utilized. This concept has the possibility of greatly improving the creep resistance of thermoplastics. Also, a new technique was developed for converting the amine functional oligomers cleanly into maleimide structures. This method involves reacting maleic anhydride with monomeric aminophenols in the presence of solvent mixtures.

Mcgrath, J. E.↗

Synthesis, curing and physical behavior of maleimide terminated poly(arylene ethers)

This paper describes the synthesis of maleimide terminated poly(ether ketones) using the solution imidization process described by Summers et al. (1987). Amorphous poly(arylene ether ketones), as well as poly(arylene ether sulfones, of controlled end group functionalities and molecular weights were synthesized by nucleophilic step polymerization of bisphehol-A phenolates with activated halides, such as 4,4'-difluorobenzophenone, and 'monofunctional' end cappers such as m-aminophenol. The thermal properties of the system included glass transition temperature (Tg) values of 160-170 C, with modulus above Tg proportional to cross-link density, which in turn was reciprocally related to oligomer molecular weight. The measurements of the fracture toughness values showed the materials to be very ductile, with the toughness increasing with oligomer molecular weight.

Lyle, G. D.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are disclosed for tetraalkyls, tetraacids, and dianhydrides substituted 1,1,1-triaryl 2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl 2,2,2-trifluoroethane, (2) 1,1-bis (dicarboxyaryl) 1-aryl 2,2,2-trifluoroethane, or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl 2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by the oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or aklyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

The full-scale process and design changes for elimination of insulation edge separations and voids in tang flap area

Qualification of the full-scale process and design changes for elimination of redesigned solid rocket motor tang nitrile butadiene rubber insulation edge separations and voids was performed from 24 March to 3 December 1990. The objectives of this test were: to qualify design and process changes on flight hardware using a tie ply between the redesigned solid rocket motor steel case and the nitrile butadiene rubber insulation over the tang capture features; to qualify the use of methyl ethyl ketone in the tang flap region to reduce voids; and to determine if holes in the separator film reduce voids in the tang flap region. The tie ply is intended to aid insulation flow during the insulation cure process, and thus reduce or eliminate edge unbonds. Methyl ethyl ketone is intended to reduce voids in the tang flap area by providing better tacking characteristics. The perforated film was intended to provide possible vertical breathe paths to reduce voids in the tang area. Tang tie ply testing consisted of 270 deg of the tang circumference using a new layup method and 90 deg of the tang circumference using the current layup methods. Tie ply process success was defined as a reduction of insulation unbonds. Lack of any insulation edge unbonds on the tang area where the new process was used, and the presence of 17 unbonds with the current process, proves the test to be a success. Successful completion of this test has qualified the new processes.

Danforth, Richard A.↗

Fiber/matrix adhesion in graphite/PEKK composites

Experiments with poly ether ketone ketone (PEKK) resin and AS-4, IM-7, and G30-500 fibers showed excellent correlation between resin/fiber contact angle and composite transverse flexural strength as measures of resin/fiber interfacial strength. Both tests indicate the strongest interface for G30-500/PEKK followed by IM-7/PEKK and AS-4/PEKK. Also discussed are fiber effects on interlaminar fracture and on the in situ crystallization of the matrix during composite fabrication.

Bucher, R. A.↗

Substituted 1,1,1-triaryl 2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures to tetraalkyls, tetraacids, and dianhydrides substituted 1,1,1-triaryl 2,2,2-trifluoroethanes which comprises: (1) 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethane, (2) 1,1-bis(dicarboxyaryl) 1-aryl-2,2,2-trifluoroethane, or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Properties of powder-impregnated graphite/PEKK

Poly Ether Ketone Ketone (PEKK) powders were prepregged on AS4 (12K), IM7 (12K), and G30-500 (12K) carbon fibers and consolidated into unidirectional laminates. The preferred formulation of PEKK for the dry powder process was identified. Mechanical test data on panels prepared via the powder process agreed well with flex, short beam shear, and double cantilever beam values obtained previously on melt-impregnated material. IM7/PEKK composites showed superior mechanical properties to AS4/PEKK and G30-500/PEKK composites. Transverse flexural strength and fiber/resin contact angle correlated well as measures of the fiber/matrix interfacial strength.

Bucher, R. A.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are given for tetraalkyl, tetraacid and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethane; (2) 1,1-bis (dicarboxyaryl) 1-aryl-2,2,2 trifluoroethane; or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Substituted 1,1,1-Triaryl-2,2,2-Trifluoroethanes and Processes for their Synthesis

Synthetic procedures to tetraalkyls. tetraacids and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1.1-bis(dialkylaryl)-1-aryl-2,2,2 -trifluoroethane, (2) 1,1-bis(dicarboxyaryl)-1-aryl-2.2,2- trifluoroethane or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl)-1-aryl-2,2,2- trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anihnes. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.↗

Measurements of Oxygenated Organic Chemicals In the Pacific Troposphere During TRACE-P: Higher Aldehydes (less than C(sub 1)), Their Sources, and Potential Role In Atmospheric Oxidation

Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.

Singh, Hanwant B.↗

Micro-machined planar field asymmetric ion mobility spectrometer as a gas chromatographic detector

A planar high field asymmetric waveform ion mobility spectrometer (PFAIMS) with a micro-machined drift tube was characterized as a detector for capillary gas chromatography. The performance of the PFAIMS was compared directly to that of a flame ionization detector (FID) for the separation of a ketone mixture from butanone to decanone. Effluent from the column was continuously sampled by the detector and mobility scans could be obtained throughout the chromatographic analysis providing chemical inforrmation in mobility scans orthogonal to retention time. Limits of detection were approximately I ng for measurement of positive ions and were comparable or slightly better than those for the FID. Direct comparison of calibration curves for the FAIMS and the FID was possible over four orders of magnitude with a semi-log plot. The concentration dependence of the PFAIMS mobility scans showed the dependence between ion intensity and ion clustering, evident in other mobility spectrometers and atmospheric pressure ionization technologies. Ions were identified using mass spectrometry as the protonated monomer and the proton bound dimer of the ketones. Residence time for column effluent in the PFAIMS was calculated as approximately 1 ms and a 36% increase in extra-column broadening versus the FID occurred with the PFAIMS.

NASA Discipline Life Sciences Technologies↗

Diels-Alder Trapping of Photochemically Generated Dienes with Acrylic Esters: A Novel Approach to Photocured Polymer Film Development

Diels-Alder cycloadditions have often been utilized in polymer synthesis as an alternative to condensation reactions. In our earlier efforts, we developed a new method for the preparation of linear aromatic polyimides, which employs o-quionodimethanes (o-QDMs), generated by a well-known photochemical reaction: the photoenolization of o-methylphenyl ketones. Photolysis of o-methylbenzophenone 1 produces hydroxy-o-quino- diemthane 2, which can be trapped with dienophiles, such as dimethyl acetylenedicarboxylate, to efficiently yield the corresponding cycloadduct (Scheme 1). Here we extend this approach to a novel photocuring process for development of polymer films. We synthesized a series of molecules with multi o-mehtylphenyl ketone functionalities. We further investigated these molecules as photoreactive monomers to obtain polyester films through Diels-Alder cycloadditions.

Ilhan, Faysal↗

Novel Ultraviolet-Light-Curable Polyimides

Polyimides have found broad application in fiber-reinforced composites for aerospace components and as thin films for electronics packaging. Typical routes to processing these materials require temperatures above 200 C. As a result, tooling costs for fabricating components from these composites can be quite high. Recent efforts within the Polymers Branch at the NASA Lewis Research Center have been aimed at developing radiationcurable (with light or electron beams) polyimides. Such materials may enable the processing of polymers and composites at or near room temperature, leading to reduced tooling requirements and costs. A new Diels-Alder route to polyimides has been developed that employs ultraviolet light (UV), rather than heat, to effect polymerization. This approach, which can be carried out at room temperature, is based on a well-known photochemical reaction--the photoenolization of o-methylphenyl ketones. Irradiation of o-methylphenyl ketones, such as 1 in the preceding figure, with UV wavelengths above 300 nm produces a photoenol, 2. This photoenol is unstable, but it persists long enough to undergo Diels-Alder reactions with good dienophiles, such as maleimide, 3. By utilizing a diketone, such as 2,5-dibenzoylp-xylene, 5, and a bismalemide, 6, this chemistry has been used to make a number of polyimides, 7.

Meador, Michael A.↗